Ernst stocker



Patented Jan. 24, 1933 UNITED STATES PATENT OFFICE.

ERNST STOCKER, F BASEL, SWITZERLAND, ASSIGNOR T0 MUNITEX CORPORATION, OI PATERSON, NEW JERSEY, A CORPORATION OF NEW JERSEY METHOD OF TREATING CELLULO SIO FIBERS R 'o Drawing. Application filed January 2,), 1930, Serial No. 424,460, and in Germany February 20, 1929.

This, invention relates to a process for treating cellulosic fibers and more partlcularly to a process of changlng the luster and/or dyeing properties of. cellulosic fibers such as cotton, vegetable fibers, artificial silk produced from cuprammonium cellulose, cellulose nitrate or viscose.

Prior to this invention, cellulosic fibers were rendered immune to substantive dyestufi's by treating said fibers with an alkalizing medium and subsequent to removing the excess alkali, treating the alkalized fibers with an esterifying reagent such as sulphochlorides of the non-substituted and substituted aromatic hydrocarbons, for instance, benzo-sulpho-chloride, ortho-tolrol-sulphochloride, xylol and naphthalene-sulpho-chloride and with chlorine, bromine or nitro derivatives of all these compounds as well as halogen phosphorous compounds. In these processes the alkalizing medium was either an aqueous solution to which was added soaps and salts of sulphonated fatty acids, if desired, or an alcoholic solution. When an aqueous alkalizing medium was used, the alkalizing was carried out at atemperature between 50-60 C. With this process it was impossible to obtain evenly immunized fibers. This was due to the face that the fibers impregnated with the aqueous alkali solution had a repulsive effect on the esterifying agent whereby the reaction was not efiected uniformly. The use of an aqueous alkalizing medium also occasioned considerable shrinkage which, of course, was highly undesirable. In the processes wherein alcoholic alkalizing mediums were used a complicated and expensive apparatus was necessary. Furthermore, there was a considerable loss of alcohol through evaporation. Another disadvantage resulted from the reaction of the alcohol and the esterifying chlorides, whereby the corresponding esters and alkali salts of the decomposed acid chlorides were formed.

I have found that I can overcome the above mentioned disadvantages and produce uniform and evenly treated cellulosic fibers by using an aqueous alkalizing medium at a relatively high temperature.

It is, therefore, an object of this invention 'phuryl chloride, may be used as the esterifying agent if deto provide a method of changing the dyeing properties and/or luster of cellulosic fibers which comprises treating the cellulosic fibers with an aqueous alkalizing medium at a rela tively high temperature and then esterifying said alkalized cellulosic materials.

Other objects will appear from the following description and appended claims. I

As above stated, the method constituting this invention comprises treating cellulosic materials with an aqueous alkalizing medium at a relatively high temperature and then treating the alkalizing -materials with an esterifying agent of the type hereafter described. In carrying out the process the cellulosic material is treated with an aqueous alkalizing medium at a relatively high temperature, for instance at least 100 C. The surplus alkalizing medium is then removed from the fibers in any suitable manner and preferably while the materials are still hot. I have obtained satisfactory results by whizzing the materials until they contain from about 40% to 80% of the liquid. It is to be understood that the whiz zing may be carried out to remove more or less of the liquid as desired. The thus alkalized materials are then treated with esterifying agents. The esterifying agents may comprise solutions of carboxyand sulpho-chlorides of nonsubstituted and substituted aromatic hydrocarbons such as benzoyl-chloride, benzo-sulpho-chloride, ortho toluol sulpho-chloride, xyloland naphthalene-sulpho-chloride and with chlorine, bromine and nitro derivatives of all of these compounds. Also inorganic compounds such as halogen phosphorous compounds, sulthionylchlorideand the like sired. It is desirable that the said esterifying solutions be substantiallyfree from water. The esterifying agent may be used over and over again since the excess is not decomposed. For certain fibers it is desirable to add to the alkalizing mediums small amounts of oxyoompounds of the aromatic or alicyclic series, for instance, cresol, cyclohexanol, etc. or mixtures of these.

The following specific examples illustrate the manner in which the method may be caring medium.

ried out. It is to be understood that these Example lI.-The alkalizing is carried. out under the same conditions as set forthin Example I using, however, a 14% solution of caustic potash containing .5% of cresol. The esterification is carried out as set forth in Example I.

Emample llI.Bleached mercerfzed cotton is alkalized as in Example I for 30 minutes, whizzed hot until it shows an increase in weight of approximately Itis then treated with a solution of 1% of phosphorous oxy-chloride in xylol at 20 C. for 30 minutes in a volume of 1 to 40.

Example I V.-Bleached yarn is alkalized with a boiling caustic soda solution as set forth in Example I and esterified in a toluol solution of 2.5% benzoyl-chloride at 30 C. in a volume of 1 to 20 for 30 minutes.

The process described above can be used to treat cellulosic fibers such as artificial silk produced from cellulose nitrate, cuprammonium or viscose. undyed loose cotton, skeins, bobbins, cops, mercerized yarns, and other vegetable fibers. The fibers treated are evenly and uniformly immunized. Due to the alkalization at a relatively high temperature shrinkage is at a minimum. The fibers no longer can be dyed with direct dyestuffs and for this reason are suitable for the manufacture of effect threads. As above stated, this process changes the luster of the materials treated. In numerous instances, especially in the case of nercerized yarns, a better whiteness and an increased luster, as compared to that obtained by the prior methods, may be obtained. In the case of artificial silk the original luster thereof or a decreased luster of any degree may be obtained, depending on the concentration of the alkaliz Thus, for instance, with a 10% aqueous alkalizing medium a dull or mtitt sheen is obtained. WVith a 2% aqueous alkalizing medium the original lust'er of the artificial silk is substantially not modified. Also the fibers possess better dyeing properties with respect to the various dyestuffs, as for instance, the socalled acetate dyestuffs.

The process above described treats cellulosic fibers or yarns. These yarns may be used in the manufacture of mixed fabrics, whereby by cross-dyeing various ornamental effects maybe obtained. It is within the scope of this invention to treatthe entire surfaces or predetermined areas of fabrics containing cellulosic yarns or threads. Thus, by treating predetermined areas of fabrics brilliant pattern effects may be produced on a dulled background or vice-versa. If desired, such fabrics may be cross-dyed, thereby producing materials of ornamental appearance.

I claim:

1. A method of changing the properties of cellulosic fibers or fabrics containing the same which comprises treating said fibers with a boiling aqueous alkali solution and esterifying the alkalized fibers with a member of the group consisting of carboxy and sulpho-chloride compounds of non-substituted and substituted aromatic hydrocarbons, inorganic sulpho-chloride compounds and phosphorous halogen compounds.

2. A method of changing the properties of cellulosic fibers or fabrics containing the 1 same which comprises treating said fibers with an aqueous alkali solution at not less than 100 C. and then esterifying the alkalized fibers with a member of the group consisting of carboxy and sulpho-chloride com pounds of non-substituted and substituted aromatic hydrocarbons, inorganic sulphochloride compounds and phosphorous halogen compounds.

3. A method of changing the properties of cellulosic fibers or fabrics containing the same which comprises treating said fibers with an aqueous alkali solution at not less than 100 (1., removing the excess solution and esterifying the alkalized fibers with a member of the group consisting of carboxy and sulpho-chloride compounds of non-substituted and substituted aromatic. hydrocarbons, inorganic sulpho-chloride compounds and phosphorous halogen compounds 4. A method of changing the properties of cellulosic fibers or fabrics containimg the same which comprises treating said fibers with an aqueous alkali solution at not less than 100 C., removing the excess of said solution until the fibers show an increase in weight of between 40% to 80%,.and thenv esterifying the treated fibers with a member of the group consisting of carboxy and sulpho-chloride compounds of non-substituted and substituted aromatic hydrocarbons, in-

cellulosic fibers or fabrics containing the same which comprises treating said fibers with an aqueous alkaline solution containing oxy-compounds of the aromatic or alicyclic series, said solution being at approximately its boiling point, removing the excess solution and esterifying the treated fibers with a member of the group consisting of carboxy and sulpho-chloride compounds of non-substituted and substituted aromatic hydrocarbons, inorganic sulpho-chloride compounds and phosphorous halogen compounds.

7. A method of changing the properties of cellulosic fibers or fabrics containing the same which comprises boiling said fibers in an alkalizing medium and treating the alkalizedvmaterial with a solution containing an aromatic sulpho-chloride.

8. A method of chan g the properties of cellulosic fibers or fa i' i cs containing the same which comprises boiling said fibers in an alkalizing medium and treating the alkalized material'with' a solution containing benz'oyl chloride.

9. A method of changing the properties of cellulosic fibers or fabrics containing the same which comprises boiling said fibers in an alkalizing medium and treating the alkalized material with a solution containing phosphorous oxy-chloride.

In testimony whereof, I have aflixed my signature to this specification.

. ERNST STOCKER. 

